Stabilization of printing pastes containing diazonium salts



Patented Aug. 23, 1949 iJNlTED STATES PATENT OFFICE STABILIZATION OF PRINTING PASTES CONTAINING DIAZONIUM SALTS No Drawing. Application May 11, 1945, Serial No. 593,312

18 Claims. (Cl. 8-71 This invention relates to compositions containing ice color diazo components, diazotized or undiazotized, and to methods of preventing the thinning of printing pastes containing such diazo components.

Producing prints of ice colors on various vegetable fibers often is effected by padding the goods with an alkaline solution of an azoic coupling component and printing with a printing paste containing diazotized ice color diazo components either freshly prepared or in the form of stabilized diazonium salts. This is a well known cheap process for producing azoic prints and requires no difiicult treatment. However, it is open to a very serious disadvantage. The printing pastes containing the diazonium salts, stabilized or unstabilized, do not keep well and particularly tend to thin out rapidly, losing their desired printing consistency. It is this thinnin action with which the present invention is concerned.

According to the present invention the diazonium salt, either in stabilized form or freshly prepared, is associated with a water soluble acid amide in which at least one of the amide hydrogens is replaced by an organic radical having at least one oleflnlc double bond or an acetylenic triple bond.

When an aromatic amine is diazotized in acid solution, a diazonium salt is formed which is generally assumed to have the following formula:

ArN -X- m where Ar stands for the aromatic radical of the diazo component and X stands for the anion of the acid. These diazonium salts are salts of the very strong diazonium bases and the aqueous solutions contain essentially the diazonium cations and the anions of the acid used, as indicated by the formula. Some of these diazonium salts are diflicult to isolate because of their great solubility. Others are not so soluble and can be easily isolated. Some are difllcult to handle after isolation because of their explosiveness; others are rather stable and do not present an explosive hazard. It is also known that if the anion of the acid X- is properly chosen, in almost all cases diazonium salts of lower solubility may be produced and therefore isolated, and it is also known that many of these diazonium salts have lost their explosive character and can be stored and handled in the dry state without danger; this kind of diazonium salt is sometimes referred to as "stabilized diazonium salts. They comprise such 2 compounds as certain aromatic sulfonates, without olefinic double bonds, borofluorides, and particularly salts of complex acids sometimes referred to as double salts, the most important of them being the double salts of diazonium chlorides and zinc chloride which correspond to the formula:

ArN (211Gb) It should be borne in mind that also these stabilized diazonium salts including the above mentioned double salts are true diazonium salts, i. e. the aqueous solution contains the same diazonium cations as the solution of any other diazonium salt derived from the same base.

The present invention deals with inhibiting the thinning action of diazonium salts only and not with any similar action that might be observed with other types of diazo compounds. While it is not intended to limit the present invention to any theory of action, I believe that it is highly probable that lowering of viscosity of printing gums is essentially caused by the diazonium cation because the same kind of thing results regardless of the anion of the diazonium salt and even the double salts of the stabilized diazonium salts described above exert a similar thinning action. Presumably in aqueous solution the stabilized diazonium salts are ionized to give the same diazonium cation. The pH of the printing paste is not critical so long as it is on the acid side, for the present invention does not deal with any other types of pastes. Alkaline medium, as is well known, causes rearrangement of the diazonium salts to diazo compounds of difierent structure.

While not desiring to limit the invention thereto, I believe that the evidence strongly indicates that the thinning action is a colloidal phenomenon rather than a chemical reaction. The. following test was made:

A diazonium salt derived from 2-nitro-4-methoxy aniline was added to a printing paste made up with a starch thickener; after 20 hours the then water thin solution was coupled with an alkaline solution of beta-naphthol and the azo dye formed was removed by filtration. The amount of azo dyestuff obtained indicated that the bulk of the diazonium salt was undecomposed and had reacted, and the filtrate still showed the reaction of starch and not the reactions of reducing sugars.

The thinnin action differs widely and depends upon the structure of the diazo component the diazonium salt derives from. I have found that um salts derived from ice color diazo components.

that is to say, from all diazotizable aromatic amines free from solubilizinggroups useful in making ice colors or azoic pigments. Typical are the following: p a Aniline and its homologues, as e. g. the toluidines, 2,4-dimethylaniline; halogen derivatives of The diazonium salts deriving from o-nitraniline thin more than those deriving from the meta and para compounds. On the other hand the diazonium salts deriving from the 2-methyl-4-ch1oroaniline and from o-anisidine have only little thinning action. Obviously, the rate of the thinning depends upon the concentration of the diazonium ions present in the printing paste.

The thinning action has been observed with all thickeners prepared from materials of vegetable origin such as starches, gums, alkyl celluloses, etc. Wheat starch, corn starch, rice starch, sweet potato starch. tapioca starch and chlorinated starch may be mentioned as examples of starches, carob bean gum and gum tragacanth may be mentioned as examples of gums, and methylor ethyl-cellulose as examples of allwl celluloses.

Obviously, also mixtures of these materials are quite oftenused in thickeners and their viscosity is equally influenced by diazonium salts. It will be noted that all of these thickeners are carbo hydrates or carbohydrate derivatives. In the claims the expression carbohydrate thickener is used in a broad sense to cover pure carbohydrates and derivatives.

I have found that water soluble acid amides in which at least one of the amide hydrogens is replaced by an organic radical containing at least one oleflnic double bond or an acetylenic. triple bond delays the thinning to such an extent that it becomes harmless at least from a practical standpoint. It is not intended to limit the present invention to any theory of action of the thinning inhibitor, but it seems reasonably certain that the eilect of the inhibitor is due at least primarily to the organic radical containing the double bonds or triple bonds and the following is advanced as a probable hypothetical explanation of the operation of the present invention without intention to restrict it thereto.

I believe that the diazonium cations which are the active thinning agents are unsaturated and have a marked tendency to combine. This unsaturated character is probably responsible for the ease with which they combine with coupling components to form azo dyestufis. When an unsaturated thinning inhibitor such as an unsaturated acid amide is'added to the diazonium salts solution before the printing thickener is added, it is probable that the diazonium cation forms a loose complex with the thinning inhibitor which decreases the aflinity of the diazonium cation and inhibits its action upon the thickener. When the thickener is first added to the diazonium salt solution followed by addition of the thinning inhibitor, thinning is prevented to a much lesser degree. Apparently in such a case the diazonium salt has already commenced its thinning action on the thickener and the action is not reversible so that the addition of the thinning inhibitor does not remedy the damage already done.

The present invention includes all the diazoniill aniline and of its homologues, as e. g. the monofil10roanil1nes, the monochloranilines, 2,5-didacroaniline, 2-fiuoro-5-chloroaniline, 2,5-dichloroaniline, m-aminobenzotrifluo'r'ide, p-amino-benzotrifluoride, 3-amino-4-chlorobenzotrifiuoride, 2-methyl-3-chloroaniline, 2-methyl-4-chloroaniline, 2-methyl-5-chloroaniline, 3-methyl-4- chloroaniline, 5-methyl-2-chloroaniline, 2-methyl-4- chloro-fi-bromoaniline, 2-methyl-4,5-dichloroaniline, 4-methyl-2,5-dichloraniline; nitro derivatives of aniline and of its homologues and their halogen derivatives, as e. g. the nitro-anilines, 2-

methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 4-methyl-2-nitroaniline, 2-nitro-4fluoroaniline. 2-nitro-4-chloroaniline, 3-nitro-4-chloroaniline. 4-nitro-2-ch1oroaniline; ether derivatives of primary aromatic amines and their halogen derivatives, as 'e. g. o-anisidine, 2-methoxy-5-methylaniline, 2,5-climethoxy-aniline, 2-methoxy-1- naphthylamine, z-amino-diphenylether, 2-amino-4-acetyl-diphenylether, benzyl-2-aminophenyl-ether, 3-fluoro-4-methoxyaniline, 2-methoxy- 5-chloroaniline, 2,5 dimethoxy-4-chloroaniline,

2-methoxy-4-chloro-5-methylaniline, 2 meth-' oxy-5-bromoaniline, 3-bromo-6-ethoxy-aniline, 4 chIoro-Z-amino diphenylether, 4 amino-2- chlorodiphenylether, 4-amino-4'-chloro-diphenyl ether, 4,4 dichloro 2 amino diphenylether,

4,4-dichloro-2-amino-diphenylether, 2,2',5'-trichloro-4-aminodiphenylether; ether derivatives of aniline and its homologues containing nitro groups as e. g. 2-methoxy-4-nitroaniline, 2-methoxy-5-nitroaniline, 2-nitro-4-methoxy-aniline, 2- methoxy-4-nitro-5-methyl-aniline; monoacyl derivatives of aromatic diamines, as e. g. N-hexahydrobenzoyl-p-phenylene diamine, N-hexahydrobenzoyl-p-toluylene diamine, N-benzoyl-pphenylene diamine; monoacyl derivatives of diamino-phenol ethers as e. g. 2-benzoylamino-4- aminoanisole, Z-hexahydrobenzoylamino-5-aminoanisole, 2-amino-5-benzoylamino hydroquinonedimethylether and diethylether, 2-amino-5- hexahydrobenzoylamio-hydroquinone dimethylether and diethylether, 2-amino-5-butyrylaminohydroquinone dimethylether and diethylether, 2- amino-5-phenoxyacetylamino-hydroquinone diethyl ether, the monomethyl and the monobenzyl and the monophenyl-urethane of 2,5- diamino-hydroquinone dimethylether and diethylether, 1 amino 3 benzoylamino 4,6-dimethoxy benzene; analogous monoacyl derivatives of 2,5-diamino-4-alkoxy-toluenes and of 2,5-diamino-4-alkoxy-chlorobenzenes and of 2,5 diamino 4 alkoxy benzene sulfodialkylamides; analogous monoacyl derivatives of 1,3-diamino-4,5-dimethylbenzene'; the diethylamide of 2 amino 4(4 chlorophenoxy) benzoic acid; monoacyl derivatives of diamino-p-chlorophenyl ethers as e. g. 2-amino-4-chloro-5-acetylaminodiphenylether, 2-benzoylamino-4-chloro-5-aminoanisole; amino derivatives of aromatic sulfones as e. g. 3-amino-4-methyl-diphenyl sulfone, 2- amino-4'-methyl-diphenyl sulfone, 2-amino-4- acetyl-diphenyl sulfone, the ethyl ester of 3- amino-4-(p toluene sulfonyl) benzoic acid, 4- methoxy-3-amino-phenyl-ethyl sulfone, i-methoxy-3-amino-phenyl) -benzyl sulfone, 4-ethoxy.

3-amino-dipheny1 sulfone, 2-amino-4-(trifluoromethyl) -phenyl-ethyl sulfone; amino derivatives of aromatic dialkylsulfonamides as e. g. 3-aminod-methyl-benzene dimethyl-sulionamide and diethylsulfonamide, 3-amino-4-methoxy-benzene diethylsulfonamide; xenylamine; alpha and beta naphthylamine; alpha amino anthraquinone; 2-amino-3-nitro-fluorene and 2-amino-3-nitrofluorenone; amino-diarylamines and their ether derivatives and their nitro derivatives as e. g. z-methoxy-S-amino-diphenylamine, 4-methoxy- 4'-amino-diphenylamine, 4-ethoxy-4-amino-diphenyl-amine, 3,4'-dinitro 4 amino-diphenylamine; amino-azo compounds, as e. g. 3,2'-dimethyl-i-amino-azobenzene, 2-methyl-4-amino- 5-methoxy-4'-chloroazobenzene, 4-amino-4f-nitro-3-methoxy-6.-methyl-azo benzene, 4-amino- 4'-nitro-2,5-dimethoxy-azobenzene, 4-amino-4- chloro-3-methoxy-6-methyl-azobenzene, the azo dye: diazotized o-anisidine coupled onto alpha naphthylamine.

There are also diazonium salts deriving from aromatic diamines in which only one of the amino groups is diazotized and they also fall within the scope of the present invention. An example of this type of amine is 2,6-dichloro-l,4- phenylene diamine. Diazonium salts deriving from diamines in which both amino groups are diazotiaed to form tetrazo compounds fall within its scope. Typical amines of this class are pphenylene diamine, benzidine, o-tolidine, o-di anisldine, 4,4'-diamino stilbene, diphenylamine, 2,2-dimethyl-4,4'-diamino diphenylamine and 1,5-diamino naphthalene.

Also diazonium salts deriving from heterocyclic amines or diamlnes fall under the present invention. Typical heterocyclic amines are Z-aminocarbazole, 3,6-diaminocarbazole, 2-nitro-3-aminocarbazole, 2 nitro 3 amlnodibenzofuran, 2- amino-3-nitrobenzothiophene, l-amino-fi-fluorobenzothiazole.

Obviously also mixtures of different diazonium salts may be used.

The inhibitors claimed in thisinvention include all the water soluble acid amides having at least one amide hydrogen replaced with an organic radical containing the olefinic double bond or acetylenic triple bond. The particular nature of the acid does not appear to be of major d,4'-diamino significance, and there are included not only the acyl radicals of organic acids, such as carboxylic and sulfonic acids, but also the acid radicals of inorganic acids, such as sulfuric acid and phosphoric acid. The compounds may be considered as represented by the following formula:

A-N-Ac in which A is an organic radical containing at least one oleflnic double bond or an acetylenic triple bond, X stands for hydrogen, alkyl or an organic radical containing at least one oleflnic 6 acid, N-allyl amido phosphoric acid of the follow ing formula:

cm=cn-cm-nnr=oion i and bis-flsallyl amide phosphoric acid of the following, formula:

The amides of organic carboxylic acids may be represented by the following formula:

in which A is an organic radical containing at least one oleflnic double bond or an acetylenic triple bond, X stands for hydrogen, alkyl, or an organic radical containing at least one oleflnic double bond or acetylenic triple bond, and R is any organic radical which does not react with or decompose diazo compounds and which is of insufficient molecular weight to render the amide water insoluble. In general the compounds in which R is a short chain alkyl or alkoxyl group are preferred, such as ethyl, methyl, ethoxy or methoxy. Other suitable amides are those in which R is the radical of a carboxylic acid, salt or ester which will confer sufficient water solubility on the compound to permit its action as a. thinning inhibitor.

Typical examples of carboxylic acid amides are: N-allyl acetamide, N-methallyl acetamide, N,N- diallyl acetamide, lLN-dimethallyl acetamide, N-allyl-N-methyl acetamide, N-allyl-N-ethyl acetamide, N-allyl propionamide, N-allyl urethane, N-methallyl urethane, N-allyl oxamic acid, the ethyl ester 'of N-allyl oxamic acid, N-allyl succinamic acid, N-methallyl succinamic acid, sym. diallyl oxamide, N-allyl benzamide m-sulfonic acid, N-methallyl monoainide of terephthalic acid, and N-allyl-3,6-disulfo-1-naphthamide. The aromatic carboxylic acid amides above mentioned are typical, it being necessary to bear in mind that the aromatic amides must be free from hydroxyl or amino groups which would make the compound capable of azoic coupling. The molecular weight of the organic carboxylic acid amides is often such that the presence of other solubilizing groups, such as sulfonic or carboxylic acid groups, is necessary so that the amide as a whole 'is still soluble and hence useful as a thinning inhibitor.

Another group of water soluble organic acid amides is the water soluble sulfonamides which are represented by the formula:

in which A is an organic radical containing at least one olefinic double bond or an acetylenic triple bond, x stands for hydrogen, alkyl, or an organic radical containing at least one olefinic double bond or an acetylenic triple bond, R is any organic radical which does not react with or decompose diazo compmmds and which is of suiflcient molecular weight to render the amide water insoluble. Where R is an aromatic radical such as one of the benzene or naphthalene series it must possess additional solubilizing groups so that the amide will be water soluble and, of course, as in the case of the carboxylic acid amides the organic radical must be free from groups which permit azoic coupling. Typical sulfonamides are: Benzoic acid m-N-allyl sulfonaimide, benzoic acid m-N-methallyl sulfonamide, m-sul-fo benzene r N-allyl sulfonamide. methane N-alM sulfonamide, N-allyl mono amide of naphthalene 2,6-disulfonic acid.

It has been found that the anti-thinning action of the amides decreases when the molecular weight of the amide becomes too high. While beyond fifteen carbon atoms some inhibiting action remains, it has become too slight to be of practical value.

' It is an advantage of the present invention that the inhibitors do not have to be added to the composition at any particular stage of its preparation. Thus they may be added before or after the diazotizable amine is diazotized. When the inhibitor is to be blended with the diazo component before diazotization it is preferable to use one which is solid at ordinary temperatures, whereas when the inhibitor is to .be added at another stage a liquid or solid product may be used with equal convenience. The diazo component, that is to say the diazotizable amine, may be blended as such with the inhibitor or, as an obvious equivalent, a diazotizable amine salt may be blended with the inhibitor. I

Some diazonlum salts are relatively stable and may be admixed with the inhibitor, Other salts which are not so stable may be stabilized in the conventional manner, for example with zinc chloride or aromatic sulfonic acids and the stabilized product blended with the inhibitor. The same results are obtained if the inhibitor is added to a separately prepared diazo solution just before the printing paste is made up. In each case thinning of the printing gum is greatly delayed or inhibited and the large flexibility of procedure is an important practical advantage of the invention. It should be noted that while the inhibitor acts regardless of the method of incor- 8 The invention will be illustrated in greater detail in the following specific examples. which are typical illustrations. The parts are by weight.

Example 1 21.22 parts of the zinc chloride double salt of the diazonlum chloride of 3-nitro-4-amino anisole and 0.49 part of N-allyl acetamide are dissolved in water, and the resulting solution is diluted with more water until the volume is equal to that occupiedby 25 parts of water. This solution is then intimately mixed with ,75 parts of' carob bean gum containing 2.5% solid material.

In a similar manner, 1.54 parts of the zinc chloride double salt of the diazonlum chloride of 4-nitro-2-amino anisole and 0.49 part of N-allyl acetamide are dissolved in water and mixed with carob bean gum to form a printing paste.

In similar manner, 1.312 parts of the zinc chloride double salt of the diazonium chloride of 2,5-dichloraniline and 0.49 part of N-allyl acetamide are dissolved in water and mixed with 8% starch gum to form a printing paste.

These three printing pastes described above are suited for the preparation of fast color prints on cloth impregnated with ice color coupling components, such as the anilide of 2,3-hydroxy naphthoic acid. Furthermore, these printing pastes have the outstanding advantage over similar pastes which do not contain the N-allyi acetamide in that their relative viscosity, and hence their utility for textile printing, is maintained much longer than that of similar pastes which do not contain this allyl derivative. This advantage is shown in the following table. In this table the relative Viscosity measurements are the times in seconds for copper plated steel shot weighing 0.107 gram each to fall 130 millimeters poration the over-all resuitis', however, not uninthrough the pastes.

Relative Vis- Relative Vis- Time after cosity eascoslty Measmixing oi Last Relag g fi g Thinning Inhibitor Used Base Used for Diazo urement 2 moment 1 Last Rel. tive Viscosi H i f Minutes after Hour after Viscosity Measurement i3 3 Mixing Mixing Measurement 0 c Hours N-allyl acetamide S-nitl'M-amino anisole 64. 0 64. 2 l7. 5 49. 4 Bordeaux, None .410 8- 1 6. 2 l7. 5 0. 4 Do. N-allyl acetamide 4-nitro-2-amino anisole 62- 0 46. 8 4 45. 8 Reddish Scarlet. None do 47.7 21.2 4 0.4 Do. N-allyl acetamide 2,5-dichlor aniline 2 5 24.6 2 22.2 Yellowish Scarlet None d0 30- 3 l- 6 2 0. 4 Do.

fluenced by the method of formulation of the Example printing paste, because if the diazonium salt is first mixed with printing gum and the inhibitor added afterwards considerable thinning may result with very active diazonlum salts and the thinning operation appears to be irreversible. The inhibitor only acts to delay or prevent further thinning after it is added. Therefore, diazonlum salts should be associated with the thinning inhibitor before mixing with printing gum, except where the thinning action is sufliciently slow so that the reverse procedure does not produce undue viscosity changes.

In the thinning inhibitors where there is present an additional acid solubilizing group such as a carboxylic acid group or a sulfonic acid group the inhibiting action resides in the anion and the particular cation is not all important and may be hydrogen, ammonium, a metal such as sodium potassium, magnesium and the like- The cation, however, must not be of such nature as to render the compound water insoluble and must also have no decomposing action on the diazonlum salts as e. g. copper or ferrous iron would have.

1.85 parts of the zinc chloride double salt of the diazonlum chloride derived from 3-nitro-4- amino anisole and 0.4 part of N,N-diallyl acetamide are dissolved in water and the solution is diluted until the resulting volume is equal to that occupied by 25 parts of water. This solution is then intimately mixed with 75 parts of 2.5% carob bean gum. The resulting printing paste is suitable for the preparation of fast Bordeaux prints upon cotton cloth impregnated with the anilide of 2,3-hydroxy napthoic acid.

1.312 parts ofthe zinc chloride double salt of the diazonium chloride of 2,5-dichloraniline and 0.5 part of the N ,N-diallyl acetamide are dissolved in water and the resulting solution is diluted with water to a volume equal to that occupied by 25 parts of water. The resulting solution is intimately mixed with 75 parts of starch paste made by dispersing the starchy powder known to the trade as RPG Gum in hot water. This printing paste is suited for the preparation of bright yellowish scarlet printson cloth impregnated with the anilide of 2,3-hydroxy naphthoic acid, or of bright reddish orange prints on cloth impregice color coupling components. e. g. scarlet prints nated with the ortho phenetidide of 2,3-hydroxy on the anilide of 2,3-hydroxy-naphthoic acid; naphthoic acid, etc. orange prints on the ortho phenetidide of 2,3-

The relative viscosities of the printing pastes hydroxy-naphthoic acid; yellow prints on the prepared as described above decrease much more tolidide of aceto acetic acid. slowly than the relative vlscosities of similar These three printing pastes described above are pastes made up in the same manner but without much more useful for producing fast color prints the thinning inhibitor. This advantage is clearly on a technical scale than similar pastes which do shown in the following table. The relative visnot contain the thinning inhibitor. This advancosity measurements are the times in seconds for tage is seen in the following table, in which the copper plated steel shot weighing .107 g. each to relative viscosity measurements are represented fall 130 millimeters through the pastes. by the times in seconds for copper plated steel Viscosity Viscosity Thinning Inhibitor Used Base Used for Dlozo Measurement Measurement 2 minutes 2 Hours after mixing after mixing N, N-diallyl acetamide--- .i-nitro-i-amino anisole- 74. 4 63.0 None ..do 65. 8 3. 0 N, N-diallyl acetamidc- 2, 5-dichlor aniline 32. 6 27. 2 None do 30. 3 0. 4

t Ez'am le 3;:- p shot weighing approximately 0.107 gram each to 1.25 parts of the zinc chloride double salt of the fall 130 millimeters through the pastes. diazonium chloride derived from 3-nitro-4-amino The N-allyl succinamic acid used in this exanisole and 0.785 part of -N -allyl succinamic acid ample can be conveniently prepared by reacting are dissolved in water and the solution is diluted allylamine with an equimolecular quantity of to a volume equal to that occupied by 25.5 parts succinic anhydride in chloroform solution. It of water. The resulting solution is intimately can be purified by crystallizing from toluene, mixed with 75 parts of carob bean gum of 2.5% M. P. 90-92 C.

l telatiize giggly; Time alteri- L38 R 15008 y in mixing 0 t e a- Thinning Inhibitor Used Base Used for Diazo Measurement Measurement last Rel. tive Visco sity alter Mixing alter Mixing Measurement N-allylsuccinamic acid 3-nitro-4amin'o anisole 41.2 37.8 2houm 32.0 None. 37.2 3.8 2h0urs 0.8 Iltg-jallleylsuccinamic acid 4-nitr3-2-am1no anisole gimme 48.4 Nnuyi'sh'ihia'ziiic'iiIIII 'iIs'uciiib'r'ihliiiifIIIIIII 5718 5115 a 113:: 4:1; None dn 45.0 5. O 3 IlOIllS 2.3

strength. The resulting printing paste is useful Exam 1e for the preparation of fast Bordeaux prints upon cloth impregnated with the anilide of 2,3-hy- 1.85 grams of the zinc chloride double salt of dmxymaphthoic acid the diazonium chloride of 3-nitro-4-amino A mixture of 1.54 parts of the zinc chloride anisole and 0.052 part of N.N'-diallyl oxamide double salt of the diazonium chloride of 4-nitroare dissolved in sumcient water to make a volume 2-amino anisole, 1.83 parts of partially .dehyequivalent to that occupied by 25 parts of water, drated magnesium sulfate, and 0.785 part of N- and the resulting solution is intimately mixed ailyl succinamic acid are dissolved in water and wi h 75 par Of 2. Car be n um- The rethe solution is diluted to a volume equal to that Sulting printing P s ins its relative visoccupied by 25 parts of water. This solution is i y mu e r h n a mil pa te made then intimately mixed with 75 parts of 2.5% without the use of the diallyl oxamide, and hence carob bean gum. The resulting printing paste can be used for print n f st colo patterns upon produces bright reddish scarlet prints upon cloth cloth impre nated with ice color couplin mimpregnated with the anilide of 2,3-hydroxyponents for a. longer time. This is shown by the naphtholc a id, following figures, which are the relative vis- 1.312 grams of the zinc chloride double salt cosities expressed in the number of seconds reof the diazonium chloride of 2,5-dichloraniline quired for copper plated steel shot weighing 0.107 and 0.314 part of N-allyl succinamic acid are disg. each to fall 130 mm. through the pastes.

Relative Relative Relative Viscosity Viscosity Viscosity Thinning Inhibitor Used Base Used for Diazo Measurement Measurement Measurement 2 Minutes 1 Hour 2 Hours after mixing after mixing after mixing N ,N '-diallyl oxamide 3-nitro-4-am ino anisole 70. 0 43. 6 32. 2 None do solved in water and the solution is diluted to a volume equal to that occupied by 25 parts of Example 5 water. The resulting solution is then intimately 1.85 grams of the zinc chloride double salt of mixed with parts of 2.5% carob bean gum. the diazonium chloride of 3-nitro-4-amino This printing paste is useful for the production of anisole and 0.4 part of the ethyl ester of N-allyl bright fast color prints on cloth impregnated with 75 oxamic acid are dissolved in sufllcient water to 2 Minutes 1 Hour Viscosity Measurement 1 1 make a volume equal to that occupied by 25 parts of water, "and the resulting solution is intimately mixed with 75 parts of 2.5% carob bean gum.

12 e. g. Bordeaux patterns on cloth impregnated with the anilide of 2,3-hydroxy-naphthoi'c acid. 1.312 parts of the zinc chloride double salt of the diazonium chloride derived from 2,5-dichlor inti m is made up in exactly aniline and 0.5 part of N-allyl urethane are disthe i r i anne i' w i h the substitution of 0.4 solved in water and the solution is diluted to a part of the potassium salt of N-allyl oxamic acid volume equal to that occupied by 25 parts of for the ethyl ester. water. The resulting solution is then intimately 1.312 parts of the zinc chloride double salt of ed with '75 parts of starch paste conta n n the diazonium chloride of 2,5-dichloraniline and 8% of a brand of starch known to the trade as 0.334 part of the potassium salt of N-allyl oxamic RPG Gum. The resulting printing paste is useacid are dissolved in suflicient water to make a ful for the pr paration of fast color P n on volume equal to that occupied by 25 parts of cloth impregnated with ice color couplin comwater, and the resulting solution is intimately ponents. a s arlet prints n cloth im nated mixed 75 parts of 2.5% carob bean gum. with the anilide of 2.3-hydroxy naphthoic acid, Another printing paste is made up exactly as and O e p ints on 010th impregnated with the the above with the exception that 0.328 part 0111110 Phenefldide 0f ydroxy flp thoic acid. 01 the calcium salt of N-allyl oxamic acid is sub- These two printing pastes c bed above restituted for the potassium salt. tain their relative viscosity and hence their utility These four printing pastes whose preparation for the printer much longer than similar pastes is described above are particularly suited for p p r d W h u h N- llyl urethane. This fact the production of fast color prints upon cloth is demonstrated in the following table, in which impregnated with the usual ice color coupling the relative viscosities are the times in seconds components, for example, the anilide of 2,3-hyfor. copper plated steel shot weighing approxidroxy naphthoic acid. These printing pastes mately 0.107'gram to tall 130 millimeters through have the advantage over those similarly prepared the pastes.

:33 &1? LastRelative Thinning Inhibitor-Used BaseusediprDiazo urement2 last Rel. Vis- Minutesafter cosity Meas- M g uremcnt meat Hours N-allyl urethanen 3-nitro4-amino anisole 57.5 17 27.2 nnn In 58-1 17 0.4 N-allylurethane 2,5-dichloraniline 27.5 2 21.0 None (in 30.3 2 0.4

but without the thinning inhibitor in that they I Example 7 maintain their relative viscosity, and hence their utility to the printer, for a much longer period. This is shown in the following table, in which 0.964 part of benzoic acid m-N-allyl sulfonamide are slurried in 10 parts of water and neuthe relative viscosity measurements are the times tralized bareflllly wi d u e caustic soda soluin seconds for copper plated steel shot weighing 0.107 g. each to fall 130 mm. through the pastes.

tion. In this solution is then dissolved 1.22 parts Relative Relative Time after 1YIisccsity Xfiiscosity of tli'iastvliisaa- Coofif gint on easureeasurea e ve soxy Thinning Inhibitor Used Base Used for Dial ment- 2 meat 1 Viscosity ity Measutenapht oic acid Minutes Hour after Measuremen anilide after mixing mixing ment Hours Ethy ester of N-allyl oxamic 3-nitro-4-amino anisole--. 68. 6 55. 7 2 52. 8 Bordeaux.

aci rotasisiuniidsalt of N-allyl 01- .do 67.4 51-4 2 420 -Do. N23 do 65.8 10.3 2 3.0 Do. Potasium 2,5-salt of N-allyl dichlor aniline -6 29.0 3 25.5 Yellowish Sim-let.

oxamic aci Calgiaim saltofN-allyloxamic do v 53.3 33.6 3 292 Do. Niv n do 45. 0 so a as Do.

Example 6 05 chloride of 3-nitro-4-amino anisole and the re 1.22 parts of the zinc chloride double salt of the diazonium chloride derived from 3-nitro-4-amino anisole and 0.5 part of N-allyl urethane are dissolved in water and the solution is diluted to a volume equal to that occupied by 25 parts of water. The resulting solution is then intimately mixed with '15 parts of 2.5% carob bean gum. The resulting printing paste is useful for the production of fast color patterns upon cloth impregnated with ice color coupling components,

sulting solution is diluted with water to a volume equal to that occupied by 26 parts of water. This solution is then intimately mixed with '75 parts of 2.5% carob bean gum to form a printing paste which is eminently suited for the production of fast color prints upon cloth impregnated with ice color coupling components. This paste retains its relative viscosity, and hence its usefulness to the printer, much longer than a similar paste which does not contain the sodium salt auaaco of benzoic acid mN-allyl sulfonamide, as is shown by the figures in the following table:

' These figures are the times in seconds for copper plated steel shot weighing 0.107 g. each to fall 130 mm. through the pastes.

The hitherto unknown benzoic acid m-N-allyl sulfonamide is prepared by adding 1 part of benzoic acid m-sulfone chloride gradually with stirring to 1 part of allyl amine in 2.5 parts of water at ordinary temperatures. A solution of .36 parts of caustic soda in water is then added and the excess allylamine is distilled oil in vacuo. The crude product is precipitated by acidification of th residue from the vacuum distillation with hydro hloric acid. Purified by crystallization from aqueous alcohol it melts at 193 C. (corn).

Example 8 0.8 part of crude sodium N-allyl sulfamate, containing a small amount of sodium bicarbonate and sodium su1fate,.is dissolved in 10 parts of water and the resulting solution is made slightly acid to Congo red paper by the addition of a small amount of dilute hydrochloric acid. In the resulting solution is dissolved 1.25 parts of the zinc chloride double salt of the diazonium chloride derived from 3-nitro-4-amino anisole. The solution is diluted to a volume equal to that occupied by parts of water, and this solution is then intimately mixed with 75 parts of 2.5% carob bean gum. Such a paste is useful for the preparation of fast color prints upon cloth impregnated with ice color couplin components, and retains its relative viscosity better than a similar paste which does not contain the thinning inhibitor,

as is shown in the following table. In this table the relative viscosity measurements are the times in seconds for copper plated steel shot weighing 0.107 gram each' to fall 130 millimeters through the pastes.

The N-allyl sodium sulfamate used in this example is prepared as follows:

65 parts of chlorosulfonic acid is dropped slowly, with external cooling, into 250 parts of pyridine. The mixture is then stirred one hour at room temperature, and to it is added at -40 C. 28.5 parts of allyl amine. The mixture is then heated to 60-70 C. for minutes, cooled, and drowned in a solution of 100 parts of soda ash in 250 parts of water. The pyridine and unreacted allylamine are removed by steam distillation. The product, mixed with some sodium bicarbonate and sodium sulfate is precipitated from the residue by addition of several times the volume of alcohol.

14 Example 9 1.29 parts of the zinc chloride double salt of the diazonium chloride derived from 3-nltro-4-amino anisole is dissolved in 22 parts of solution containing approximately 0.7 part of bis-N-allyl amino phosphoric acid of the probable formula! This solution is then diluted with water to a volume equal to that occupied by 25 parts of water, and the resulting solution is intimately mixed with 75 parts of 2.5% carob bean gum. This printing paste, which is useful for the production of fast prints on cloth impregnated with ice color coupling components, retains its relative viscosity. and hence its utility to the printer, better than a similar paste which does not contain the thinning inhibitor. This fact is shown by the following table in which the relative viscosities are indicated by the times in seconds for copper plated steel shot weighing 0.107 gram each to fall 130 mm. through the pastes.

The solution of bis-N-allylamido phosphoric acid used in this example is prepared as follows:

20 parts of allylamine'in 60 parts of dry ether are added with stirring to 15.34 parts of phosphorus oxychloride in a vessel cooledexternally by ice. After stirring for an hour at room temperature the precipitate of allylamine hydrochloride is filtered off, and the ether is evaporated from the filtrate. The viscous oil remaining is reacted with 20 parts of water, with which it reacts vigorously. The resulting clear solution is made alkaline to Brilliant Yellow paper by a solution containing 4 parts of caustic soda, and the excess allylamine is distilled off with steam. The slightly acid residual solution contains the thinning inhibitor and is used as such without isolation of the active ingredient.

Example 10 An intimate mixture is made of 1.68 parts of 3-nitro-4-amino anisole, 0.84 part of N-allyl succinamic acid, and 0.84 part of common salt. This mixture is stirred with 15 parts of water, 6.5 parts of 5 N hydrochloric acid and enough ice to lower the temperature to 5 C., and the base is diazotized by the addition of 0.7 part of sodium nitrite dissolved in approximately two parts of water. One printing paste is made by thoroughly mixing one-half of the 'diazo solution prepared above with '75 parts of 2.5% carob bean gum; another printing paste is made by mixing one-half of the aboveprepared diazo solution with '75 parts of 8% starch paste made from the branch of starch powder known to the trade as RPG Gum. These printing pastes become thin much less rapidly'than similar pastes prepared from equivalent amounts of the same base not mixed with thinning inhibitor. For this reason, the printing pastes described above retain their utility for the printing of fast color patterns on cloth impregnated with ice color coupling components for a longer time than pastes which do not contain the inhibitor. This is shown in the following table. The relative viscosity measurements indicated below are the times in seconds for copper plated steel shot of the weight indicated to fall 13o millimeters through the paste.

16 tached to the acyl group, at least one hydrogen of the amide group being replaced with an alltiti ti id 38%?" an m 1 s y scos y soo. y e g o Thinning Inhibitor Used Gum Used Reading Reading Reading shot Used 2/4 Min 1 Hour 18 Hours Grams N-allyl succinamlc acid 2.5% carob bean 65.4 63. 6 25. 2 0. 107 None do 62-2 20. 4 l. 0 0. 107 Is-allyl succlnamic acid 8% RPG starch gum 9. 2 7. 0 4. 0 0. 35a Nmm n 14- 2 5. 0 1- 6 0- 358 This application is in part a continuation or my earlier application, Serial No. 469,566, filed December 19, 1942, and now abandoned.

I claim:

1. A composition suitable for use in the preparation of printing pastes containing carbohydrate gum thickeners comprising a mixture of an ice color forming compoundincluded in the group consisting of water soluble diazonium salts and intermediates for producing them, the intermediates consisting of diazotizable amines and amine salts, the composition further containing admixed therewith a water soluble acid amide having not more than 15 carbon atoms and having only a single amide group attached to the acyl group, at least one hydrogen oi the amide group being replaced with an aliphatic radical included in the group consisting of aliphatic radicals having an olefinic double bond and aliphatic radicals containing an acetylenic triple bond, the acid amide being free from groups capable of azoic coupling or of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazo compounds at room temperature, the amount of acid amide being suflicient to substantially inhibit thinning of a printing paste prepared from the composition.

2. A composition suitable for use in the preparation of printing pastes containing carbohydrate gum thickeners comprising a mixture of an ice color forming compound included in the group consisting of compositions containing water soluble diazonium salts and intermediates for producing said compositions, the intermediates consisting of diazotizable amines and amine salts, the composition further containing admixed therewith a water solu 1e acid amide of a carboxylic acid, this amid having not more than-15 carbon atoms and having only a single amide group attached to the acyl group, at least one hydrogen of the amide group being replaced with an aliphatic radical included in the group consisting of aliphatic radicals having an olefinic double bond and aliphatic radicals containing phatic radical included in the group consisting of aliphatic radicals having an olefinic double bond and aliphatic radicals containing an acetylenic triple bond, the acid amide being free from groups capable of azoic coupling or of reaction with nitrous acid and also free from metal compounds capable oi decomposing diazo compounds at room temperature, the amount of acid amide being suiilcient to substantially inhibit thinning of a printing paste prepared from the composition.

4. A composition suitable for use in the preparation of printing pastes containing carbohydrate gum thickeners comprising a mixture of an ice color forming compound included in the group consisting of compositions containing water soluble diazonium salts and intermediates for producing acid compositions, the intermediates consisting of diazotizable amines and amine salts, the composition further containing admixed therewith a water soluble acid amide of an organic sulfonic acid, this amide having not more than 15 carbon atoms and having only a single amide group attached to the acyl group, at least one hydrogen of the amide group being replaced with an aliphatic radical included in the group consisting of aliphatic radicals havin at least one olefinic double bond' and aliphatic radicals containing an olefinic double bond and aliphatic radicals containing an acetylenic triple bond, the acid amide being free from groups capable of azoic coupling or oi. reaction with nitrous acids and also being free from metal compounds an acetylenic triple bond, the acid amide being free from groups capable of azoic coupling or of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazo compounds at room temperature, the amount of acid amide being sufllcie'nt to substantially inhibit thinning of a printing paste capable of decomposing diazo compounds. at room temperature, the amount or acid amide being sufllcient to substantially inhibit thinning of a printing paste prepared from the composition.

5. A diazo composition useful for the preparation of printing pastes containing carbohydrate gum thickeners comprising a mixture of a water soluble diazonium salt derived from an ice color diazo component and a water soluble acid amide having not more than 15 carbon atoms and having only a single amide group attachedto the acyl group, at least one of the amide hydrogens being replaced with an aliphatic radical included in the group consisting of aliphatic radicals having an olefinic double bond and aliphatic radicals having an acetylenic triple bond, the amides being free from groups capable of azoic coupling of of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazonium salts at room temperature, the amount of the acid amide 7 being suificient to substantially inhibit the thinning of a printing paste made from the said composition.

6. A diazo composition useful for the preparation of printing pastes containing carbohydrate gum thickenerscomprising amixture of a water soluble diazonium salt derived from an ice color diazo component and a water soluble acid amide of a carboxylic acid, this amide having not more than 15 carbon atoms and having only a single amide group attached to the acyl group, at least 17 one of the amide hydro ens being replaced with an aliphatic radical included in the group consisting of aliphatic radicals having an olei'lnic azonillm salts at room temperature, the amount of the acid amide being sufllcient to substantially inhibit the thinning of a printing paste made from the said composition.

'7. A diazo composition useful for the preparation of printing pastes containing carbohydrate gum thickeners comprising a mixture of a water soluble diazonium salt derived from an ice color diazo component and a water soluble acid amide of an organic sulfonic acid, this amide having not more than 15 carbon atoms and having only a single amide group attached to the acyl group, at least one of the amide hydrogens being replaced with an aliphatic radical included in the group consisting of aliphatic radicals having an olefinic double bond and aliphatic radicals having an acetylenic triple bond, the amides being free from groups capable of azoic coupling or of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazonium salts at room temperature, the amount of the acid amide being suflicient to substantially inhibit the thinning of a printing paste made from the said composition.

8. A diazo composition useful for the prepara-,

tion of printing pastes containing carbohydrate gum thickeners comprising a mixture of a water soluble diazonium salt derived from an ice color diazo component and a water soluble acid amide of an inorganic acid having not more than 15 carbon atoms and' ha ving only a single amide group attached to the acyl group. at least one of the amide hydrogens being replaced with an aliphatic radical included in the group consisting of aliphatic radicals having an oleiinic double bond and aliphatic radicals having an acetylenic triple bond, the amides being free from groups capable of azoic coupling or of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazonium salts at room temperature, the amount of the acid amide being sumcient to substantially inhibit the thinning of a printing paste made from the said composition.

9. A printing paste containing a carbohydrate thickener, a water soluble diazonium salt derived from an ice color diazo component and a water soluble acid amide containing not more than 15 carbon atoms and having only a single amide group attached to the acyl group having at least one amide hydrogen replaced by an aliphatic radical included in the group consisting of aliphatic radicals having an olefinic double bond and aliphatic radicals containing an acetylenic triple bond, the acid amide being free from groups capable of azoic coupling or of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazo compounds at room temperature, the amount of the acid amide being suflicient to substantially inhibit thinning of the paste.

10. A printing paste containing a carbohydrate thickener, a water soluble diazonium salt derived from an ice color diazo component and a water soluble acid amide of a carboxylic acid containing not more than 15 carbon atoms and having only a single amide group'attached to the acyl group having at least one amide hydrogen replaced by an aliphatic radical included in the group consisting of aliphatic radicals having an oleflnic double bond and aliphatic radicals containing an acetyl enic triple bond, the acid amide being free from groups capable of azoic coupling or of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazo compounds at room temperature, the amount of the acid amide being sufficient to substantially inhibit thinning of the paste.

11. A printing paste containing a carbohydrate thickener, a water soluble diazonium salt derived from an ice color diam component and a water soluble acid amide of an organic sulfonic acid containing not more than 15 carbon atoms and having only a single amide group attached to the acyl group having at least one amide hydrogen replaced by an aliphatic radical included in the group consisting of aliphatic radicals having an olefinic double bond and aliphatic radicals containing an acetylenic triple bond, the acid amide being free from groups capable of azoic coupling or of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazo compounds at room temperature, the amount of the acid amide being suflicient to substantially inhibit thinning of the paste.

12. A printing paste containing a carbohydrate thickener, a water soluble diamnium salt derived from an ice color diazo component and a water not more than 15 carbon. atoms and having only a single amide group attached to the acyl group having at least one amide hydrogen replaced by an aliphatic radical included in the group consisting of aliphatic radicals having an oleflnic double bond and aliphatic radicals containing an acetylenic triple bond, the acid amide being free from groups capable of azoic coupling or of reaction with nitrous acid and also being free from metal compounds capable of decomposing diazo compounds at room temperature, the amount of the acid amide being sufllcient to substantially inhibit thinning of the paste.

13. A composition according to claim 1 in which the aliphatic radical replacing at least one of the hydrogens of the amide group contains an oleilnic double bond.

14. A composition according to claim 5 in which the aliphatic radical replacing at least one of the hydrogens of the amide group contains an oleflnic REFERENCES CITED- The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,378,276 Adams J1me 12, 1945 76 2,386,646 Adams Oct. 9, 1945 Certificate of Correction I Patent No. 2,479,890 August 23, 1949 FREDERIC H. ADAMS It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 6, lines 65 and 66, for the word sufiicient read insuficient; columns 11 and 12, Example 5, in the table, first column thereof, fourth item, for Potassium 2,5-sa1t read Potassium salt; same table, second column thereof, same line, for "dichlor ani1ine read 2,5-d'ichl0r aniline; column 14, line 6, for amino read amide;

and that the said Letters Patent should be read with these corrections therein that 1 the same may conform to the record of the ease in the Patent Ofiice.

Signed and sealedthis 7th 'day' of February, A. D. 1950.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

